Properties of thermally conductive silicone rubbers filled with admicellar polymerized polypyrrole-coated Al2O3 particles

Polypyrrole (PPy) nanolayers were introduced on the surface of alumina (Al₂O₃) particles via admicellar polymerization. The properties of silicone rubbers (SRs) filled with PPy-coated Al₂O₃ and pristine Al₂O₃ as thermally conductive fillers were studied and compared. The results demonstrate that the addition of PPy-coated Al₂O₃ leads to a better interfacial compatibility but lower cross-linking density of the composites than pristine Al₂O₃. The improvement in the compatibility and the decrease in the cross-linking density are paradoxes in affecting mechanical properties. The improvement in the compatibility shows a slight predominance on the strength at low-filler contents. Lower cross-linking density of modified-Al₂O₃/SR composites led to a better processing performance and a higher maximum filler loading amount than the pristine Al₂O₃/SR composites, which is beneficial to increasing the thermal conductivity and maintaining a relatively good strength. The PPy-coated Al₂O₃/SR composite with 83 wt% filler content has a thermal conductivity of 1.98 W/(m K) and a tensile strength of 2.9 MPa, and the elongation at break was 63%. Functionalized fillers by admicellar polymerization used in the fabrication of filler/SR composites not only improve the interfacial compatibility but also optimize and expand the functions of the composites, which has great significance for the production and application of thermally conductive SR in some branches of industry (automotive, electrical engineering, etc.) in the future.     

Novel heat‐conductive composite silicone rubber

The silicone rubber with good thermal conductivity and electrical insulation was obtained by taking vinyl endblocked polymethylsiloxane as basic gum and thermally conductive, but electrically insulating hybrid Al₂O₃ powder as fillers. The effects of the amount of Al₂O₃ on the thermal conductivity, coefficient of thermal expansion (CTE), heat stability, and mechanical properties of the silicone rubber were investigated, and it was found that the thermal conductivity and heat stability increased, but the CTE decreased with increasing Al₂O₃ fillers content. The silicone rubber filled with hybrid Al₂O₃ fillers exhibited higher thermal conductivity compared with that filled with single particle size. Furthermore, a new type of thermally conductive silicone rubber composites, possessing thermal conductivity of 0.92 W/mK, good electrical insulation, and mechanical properties, was developed using electrical glass cloth as reinforcement. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2478–2483, 2007     

Highly thermally conductive room‐temperature‐vulcanized silicone rubber and silicone grease

In this study, the effects of thermally conductive filler type (α‐Al₂O₃, SiC), volume fraction of the filler, and filler particle size distribution on the thermal conductivity and viscosity of room‐temperature‐vulcanized (RTV) silicone rubber and silicone grease were investigated. We were interested to find that silicone grease (or the RTV silicone rubber) had a maximum thermal conductivity (～1.48 W/mK) and a minimum viscosity (～3.4 × 10⁴ mPa s), with a definite total volume fraction of the filler (0.55) when the distribution of filler sizes (the number ratio of two different particles sizes, i.e., 0.8 and 6 μm) was 600–700. We were able to increase the thermal conductivity of the RTV silicone rubber and silicone grease beyond 2 W/mK by increasing the total volume fraction of the filler with adequate filler size distributions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2397–2399, 2003     

Multi-contact hybrid thermal conductive filler Al2O3@AgNPs optimized three-dimensional thermal network for flexible thermal interface materials

In this work, a multi-contact Al₂O₃@AgNPs hybrid thermal conductive filler was synthesized by in-situ growth method to fill high thermal conductivity polydimethylsiloxane (PDMS)-based composites to prepare TIMs. And the thermal conductivity, electrical conductivity, and mechanical properties of the composite materials were studied. During the synthesis process of the multi-contact hybrid filler, different concentrations of silver ions were reduced to generate silver nanoparticles and attached to the surface of Al₂O₃. Al₂O₃@AgNPs/PDMS thermally conductive composites were prepared by changing the filler addition. Using SEM, XPS, and XRD is used to characterize the morphology and chemical composition of Al₂O₃@AgNPs hybrid filler. The thermal conductivity of PDMS-based composites with different AgNPs content under 70 wt% filler loading was studied. The results show that the thermal conductivity of PDMS-based composites filled with 7owt%Al₂O₃@3AgNPs/PDMS multi-contact hybrid filler is 0.67 W/m·K, which is 3.72 times that of pure PDMS, and is higher than that of unmodified Al₂O₃ with the same addition amount. /PDMS composite material has a high thermal conductivity of 24%. This work provides a new idea for the design and manufacture of high thermal conductivity hybrid fillers for TIMs.     

Thermally conductive silicone rubber reinforced with boron nitride particle

Thermally conductive silicone rubber used as elastomeric thermal pad is successfully developed with boron nitride powder as conductive filler. The effects of content and particle size of filler on the thermal conductivity and mechanical property of silicone rubber are investigated. The results indicate that the use of hybrid boron nitride with three different particle sizes at a preferable weight ratio gives silicone rubber better thermal conductivity compared with each boron nitride with single particle size at the same total filler content. Furthermore, scanning electron microscopy, differential scanning calorimeter, thermogravimetric, etc., are used to characterize the morphology, curing behavior, thermal stability, and coefficient of thermal expansion (CTE) of the silicone rubber composites. POLYM. COMPOS., 28:23–28, 2007. © 2007 Society of Plastics Engineers     

Preparation and heat resistance of hollow glass microbead/silicone rubber composite coating

Hollow glass microbead/silicone rubber composite coatings were prepared to improve the heat-resistance and mechanical properties of silicone rubber-based composites, using CE modified SR as the matrix and HGM as the filler. The microscopic morphology and thermal stability of the composites were characterized by scanning electron microscopy (SEM) and thermogravimetric analyzer (TGA), respectively. The results showed that the thermal stability of the composites increases with the increase of filler content. For the composite sample with a HGM mass content of 16.7%, the initial decomposition temperature (T₅) is 408°C, which is 84°C higher than that of silicone rubber. The low density and high sphericity of HGM make it easier to uniformly disperse in the polymer matrix. In addition, compared to silica, which is commonly used as an inorganic filler, the lower thermal conductivity of HGM is also beneficial for achieving better thermal shielding effect. It is confirmed that the insufficient thermal stability of the polymer matrix above 400°C can be compensated for by the properly dispersed inorganic fillers. Therefore, the thermal stability of the composite is improved by the synergistic effect of modified heat-resistant matrix and inorganic filler.     

Preparation and characterization of conductive and magnetic PPy/Fe3O4/Ag nanocomposites

In this article, conductive and magnetic nanocomposites composed of polypyrrole (PPy), magnetite (Fe₃O₄) nanoparticles (NPs), silver (Ag) NPs, have been successfully synthesized with a two step process. First, the PPy/Fe₃O₄ was prepared by the ultrasonic in situ polymerization. Next, the PPy/Fe₃O₄/Ag was synthesized through the electrostatic adsorption. The products were characterized by fourier‐transform infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM), Thermogravimetric (TG), conductivity and magnetization analysis, and the results showed that the Ag NPs with the good conductivity coated uniformly on the surface of PPy/Fe₃O₄ and improved the conductivity of PPy/Fe₃O₄/Ag composites. In addition, as compared with PPy/Fe₃O₄, PPy/Fe₃O₄/Ag composites also have the excellent electro‐magnetic property and enhanced thermostability. POLYM. COMPOS., 35:450–455, 2014. © 2013 Society of Plastics Engineers     

Processability,hardness, and magnetic properties of rubber ferrite composites containing manganese zinc ferrites

Abstract

Rubber ferrite composites have the unique advantage of mouldability, which is not easily obtainable using ceramic magnetic materials. The incorporation of mixed ferrites in appropriate weight ratios into the rubber matrix not only modifies the dielectric properties of the composite but also imparts magnetic properties to it. Mixed ferrites belonging to the series of Mn_{(1 -x)}Zn_x Fe₂ O₄ have been synthesised with different values of x in steps of 0·2, using conventional ceramic processing techniques. Rubber ferrite composites were prepared by the incorporation of these pre-characterised polycrystalline Mn_{(1 -x)}Zn_xFe₂ O₄ ceramics into a natural rubber matrix at different loadings according to a specific recipe. The processability of these elastomers was determined by investigating their cure characteristics. The magnetic properties of the ceramic fillers as well as of the rubber ferrite composites were evaluated and the results were correlated. Studies of the magnetic properties of these rubber ferrite composites indicate that the magnetisation increases with loading of the filler without changing the coercive field. The hardness of these composites shows a steady increase with the loading of the magnetic fillers. The evaluation of hardness and magnetic characteristics indicates that composites with optimum magnetisation and almost minimum stiffness can be achieved with a maximum loading of 120 phr of the filler at x=0 4. From the data on the magnetisation of the composites, a simple relationship connecting the magnetisation of the rubber ferrite composite and the filler was formulated. This can be used to synthesise rubber ferrite composites with predetermined magnetic properties.     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

Preparation and construction mechanism of thermal conductive epoxy-based composite via magnetic field induced orientation

BN was modified with Fe₃O₄ to confer it with paramagnetic responsivity. The scanning electron microscopy and energy dispersive spectrometer (EDS) results demonstrated that with the assistance of an external magnetic field, the paramagnetic BN particles within an epoxy matrix are effectively aligned along the direction of the magnetic field during the curing process of epoxy resin, hence forming continuous thermal conduction pathways. Therefore, the thermal conductivity of the epoxy-based composite filled with 30 wt% of BN and externally applied with a 50 mT magnetic flux density was 0.7417 (W/m·K), an improvement of 207.89% relative to the pure epoxy resin. The establishment of continuous thermal pathways facilitates effective phonon conduction, thereby further enhancing the thermal conductivity of the material. Meanwhile, this study investigates the chain formation mechanism of Fe₃O₄-modified BN under the influence of a magnetic field. When subjected to an applied magnetic field, the magnetic BN embedded in an epoxy resin matrix undergoes magnetization, rotation, and contact. Subsequently, multiple particles initially form short chains, then aggregate into longer chains aligned with the direction of the magnetic field. The findings indicate that the magnetic field induced particle alignment method holds significant potential in the fabrication of high thermal conductivity polymer composites with low filler loading.     

石墨及其表面改性对硅橡胶导热性能的影响

用双辊混炼机将导热填料分散到聚甲基乙烯基硅氧烷中,再配以增强剂、硫化剂等,经模压硫化制得导热硅橡胶。研究了导热填料种类、石墨的表面改性和用量以及石墨与炭黑的复配对硅橡胶导热性和力学性能的影响。结果表明,在用量相同的情况下,导热填料的导热系数越高,其填充硅橡胶的导热性越好,且硅橡胶的导热系数随导热填料用量的增加而增大。石墨的表面改性改善了石墨与硅橡胶的界面相容性,使硅橡胶的力学性能和导热性都得到提高。不同粒径及颗粒形态的炭黑与石墨复合可改善硅橡胶的导热性和力学性能,导热硅橡胶的拉伸强度和扯断伸长率随复合填料中炭黑用量的增加而提高,当石墨与炭黑质量比为25/5时,硅橡胶的导热系数最高,综合性能较好。     

Novel electromagnetic interference shielding effectiveness in the microwave band of magnetic nitrile butadiene rubber/magnetite nanocomposites

A novel nitrile butadiene rubber (NBR)/magnetite (Fe₃O₄) nanocomposite for electromagnetic interference (EMI) shielding at microwave frequency was successfully fabricated. The structural features of as-synthesized magnetite and NBR/Fe₃O₄ were examined by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The number of elastically effective chains, volume fraction of rubber, interparticle distance among conductive sites, polymer–filler interaction, and porosity of the nanocomposites were evaluated. The mechanical properties, including the tensile strength, elongation at break, and hardness, of the composites were measured. The static electrical properties, such as the electrical conductivity, carrier mobility, and number of charge carriers, as a function of magnetite content were evaluated. The interrelation between the electrical conductivity, shielding effectiveness (SE), dielectric constant, and skin depth of the composites are discussed. Finally, the EMI SE versus frequency was tested. The results reveal that an SE of 28–91 dB against EMI in the 1–12 GHz range depended on the loading of the conducting magnetite within the NBR matrix. Accordingly, these nanocomposites may used in the field of microwave absorption devices. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of nanoparticles on the performance of thermally conductive epoxy adhesives

Microsized or nanosized α‐alumina (Al₂O₃) and boron nitride (BN) were effectively treated by silanes or diisocyanate, and then filled into the epoxy to prepare thermally conductive adhesives. The effects of surface modification and particle size on the performance of thermally conductive epoxy adhesives were investigated. It was revealed that epoxy adhesives filled with nanosized particles performed higher thermal conductivity, electrical insulation, and mechanical strength than those filled with microsized ones. It was also indicated that surface modification of the particles was beneficial for improving thermal conductivity of the epoxy composites, which was due to the decrease of thermal contact resistance of the filler‐matrix through the improvement of the interface between filler and matrix by surface treatment. A synergic effect was found when epoxy adhesives were filled with combination of Al₂O₃ nanoparticles and microsized BN platelets, that is, the thermal conductivity was higher than that of any sole particles filled epoxy composites at a constant loading content. The heat conductive mechanism was proposed that conductive networks easily formed among nano‐Al₂O₃ particles and micro‐BN platelets and the thermal resistance decreased due to the contact between the nano‐Al₂O₃ and BN, which resulted in improving the thermal conductivity. POLYM. ENG. SCI., 50:1809–1819, 2010. © 2010 Society of Plastics Engineers     

Comparison of four commonly used high temperature vulcanized silicone rubber formulas for outdoor insulator and their regional adaptability

High temperature vulcanized silicone rubber (HTVSR) insulators are widely used in transmission lines. In this article, four formulas [fumed silica and precipitated silica as reinforcing agent, alumina trihydrate (ATH) and alumina as flame retardant, and Fe₂O₃ and Fe₃O₄ as colorant] widely used in the production of HTVSR insulators were investigated by performing a series of laboratory experiments. The surface morphologies of silicone rubber, mechanical characterization (hardness, tensile property, and tear strength), electrical properties (volume resistivity, dielectric property, and breakdown strength), hydrophobicity and its transfer property, and thermal property of these four formulas were analyzed. According to the test results, the formula composed of fumed silica, Fe₂O₃ colorant, and alumina trihydrate (ATH) were excellent in mechanical properties because of more secondary structures, more bound rubber, and uniform dispersion. Therefore, it can be used in strong wind and bird pecking regions. Due to the absence of crystal water, the formula composed of fumed silica, Fe₂O₃ colorant, and alumina was observed to be excellent in thermal stability and electrical properties, making it suitable for the regions with high temperature and humidity. The formula composed of precipitated silica, Fe₃O₄ colorant, and ATH was found to be excellent in hydrophobicity transfer characteristics because of more raw rubber and satisfactory performance could be expected when it was applied in polluted regions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47477.     

Design and preparation of low-filled magnetic oriented BN@Fe3O4/EP insulating composite with improved thermal conductivity and thermal stability

As an excellent two-dimensional insulating material with high thermal conductivity, high temperature stability and high hardness, hexagonal boron nitride(h-BN) is widely applied in semiconductor manufacturing, aerospace, metallurgical manufacturing and other cutting-edge fields. However, the unique surface structure of h-BN leads to poor lubricity and easy agglomeration, which limits the application of h-BN especially in the field of electronic packaging. To address key issues boosted above, this study designed and prepared the BN@Fe₃O₄ magnetic insulating particles and doped it into the reduced viscosity epoxy resin to prepare the composites. By selecting appropriate external magnetic field strength and BN@Fe₃O₄ particles’ content, a novel 3D structure of fillers like dominoes in epoxy resin composite was successfully constructed. The microstructure of the BN@Fe₃O₄ particles and composites were analyzed, the thermal conductivity, the mechanical and the electrical properties of composites were simultaneously tested. Results manifested that the core-shell structures with BN as core and Fe₃O₄ as shell was successfully prepared, linking through the PDA middle layer between the BN core and Fe₃O₄ shell. Under the influence of magnetic orientation, the BN@Fe₃O₄ magnetic particles were preferred an out-of-plane oriented in the epoxy resin composites, resulted an enormously enhanced on thermal conductivity of composites. At a magnetic field strength of 60 mT and 25 vol% BN@Fe₃O₄ content, the thermal conductivity of BN@Fe₃O₄/EP composites is as lofty as 1.832 W/(m K), which is 1023.46% higher than that of pure epoxy resin. Meanwhile, the thermal stability has also been slightly improved, the elastic modulus and insulation performances remain at the same level.     

Preparation of nano‐reinforced thermal conductive natural rubber composites

Natural rubber (NR) composites highly filled with nano‐α‐alumina (nano‐α‐Al₂O₃) modified in situ by the silane coupling agent bis‐(3‐triethoxysilylpropyl)‐tetrasulfide (Si69) were prepared. The effects of various modification conditions and filler loading on the properties of the nano‐α‐Al₂O₃/NR composites were investigated. The results indicated that the preparation conditions for optimum mechanical (both static and dynamic) properties and thermal conductivity were as follows: 100 phr of nano‐α‐Al₂O₃, 6 phr of Si69, heat‐treatment time of 5 min at 150°C. Furthermore, two other types of fillers were also investigated as thermally conductive reinforcing fillers for the NR systems: (1) hybrid fillers composed of 100 phr of nano‐α‐Al₂O₃ and various amounts of the carbon black (CB) N330 and (2) nano‐γ‐Al₂O₃, the particles of which are smaller than those of nano‐α‐Al₂O₃. The hybrid fillers had better mechanical properties and dynamic performance with higher thermal conductivity, which means that it can be expected to endow the rubber products serving under dynamic conditions with much longer service life. The smaller sized nano‐γ‐Al₂O₃ particles performed better than the larger‐sized nano‐α‐Al₂O₃ particles in reinforcing NR. However, the composites filled with nano‐γ‐Al₂O₃ had lower thermal conductivity than those filled with nano‐α‐Al₂O₃ and badly deteriorated dynamic properties at loadings higher than 50 phr, both indicating that nano‐γ‐Al₂O₃ is not a good candidate for novel thermally conductive reinforcing filler. POLYM. COMPOS., 37:771–781, 2016. © 2014 Society of Plastics Engineers     

高导热室温硫化硅橡胶和硅脂

研究了Ａｌ２Ｏ３、ＳｉＣ两类导热填料以及填料的粒径分布对室温硫化硅橡胶和硅脂的导热性能和粘度的影响：发现当粒径分布适当时,可得到导热系数高、粘度低的室温硫化导热硅橡胶及导热硅脂。     

Improvement of thermo-electrical properties of polymer composites filled with multiwall carbon nanotubes decorated carbon fillers

To enhance the thermo-electrical properties of liquid silicone rubber (LSR) in applications, the carbon fibres (CFs) modified by multiwall carbon nanotubes (MWCNT) on the surfaces were used as the fillers. The MWCNT-modified CFs (MPCFs) were analysed by Fourier transform infrared spectra, thermogravimetric analysis, scanning electron micrograph and energy dispersive X-ray spectroscopy. It was found that MWCNT were successfully adsorbed onto the surface of CFs. The MPCFs functioned as conductive fillers in LSR for thermal and electrical conductivity application and exhibited significant enhancement. The effects of MPCFs loading on thermal conductivity and volume resistivity of LSR composites were investigated in detail. Results of this work revealed that the MPCFs/LSR composites possessed a thermal conductivity of 0.73?W?m^?1?K^?1 with 14?vol.-% filler loading, approximately 3.48-fold higher than that of pure LSR substrate. And with the increase of MPCFs loading, the least volume resistivity of MPCFs/LSR composites is 10?Ω?cm. Besides, compared with that of neat LSR, the tensile strength of MPCFs/LSR composites increased 0.913?MPa.     

Enhancement in electrical and thermal performance of high-temperature vulcanized silicone rubber composites for outdoor insulating applications

High-temperature vulcanized silicone rubber composites are highly desirable as outdoor insulating materials due to their immense thermal and electrical performance. The aim of this work is to study the role of co-combined fillers (modified fumed silica [MFS], titanium dioxide [TiO₂], with graphene [G]) on electrical and thermal properties of silicone rubber (S) composites. The dielectric response of S/MFS_10 phr and S/TiO₂_20 composites tailored with 2 phr G was characterized by broadband dielectric spectroscopy. The hybrid filler/composites were found to show higher thermal stability when 2 phr G was added. In addition, a low quantity of G filler was found to slightly increase the AC dielectric breakdown strength of the S/MFS_10 and S/TiO₂_20, where an improvement of 3 and 5% was found, respectively. Several steps were observed in the thermal decomposition of the S rubber composites by thermogravimetric analysis-Fourier-transform infrared spectroscopy. Our findings revealed great potentials for fabricating hybrid-filler/silicone rubber composites with enhanced electrical and thermal properties for outdoor insulating applications.     

Preparation and properties of novel,flexible, lead‐free X‐ray‐shielding materials containing tungsten and bismuth(III) oxide

Novel, flexible, lead‐free X‐ray‐shielding composites were prepared with a high‐functional methyl vinyl silicone rubber (VMQ) matrix with W and Bi₂O₃ as filler materials. To verify the advanced properties of the lead‐free material, composites with the same mass fraction of PbO were compared. With the X‐ray energy ranging from 48 to 185 keV, the W/Bi₂O₃/VMQ composites exhibited higher X‐ray‐shielding properties. As the filler volume fraction decreased, the tensile strength, elongation, tear strength, and flexibility of the W/Bi₂O₃/VMQ composites increased. The Shore hardness of the W/Bi₂O₃/VMQ composites had a maximum value of 46.6 HA and was still very flexible. With decreasing filler volume fraction, the water‐vapor transmission performances of the W/Bi₂O₃/VMQ composites increased, and the W/Bi₂O₃/VMQ composites also showed better water‐vapor permeability. The heat‐transfer properties of the W/Bi₂O₃/VMQ composites increased with increasing W content, and when the W content exceeded 70 wt %, the thermal conductivity of the W/Bi₂O₃/VMQ material was about 70.45% higher than that of the PbO/VMQ composite. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43012.